US4472581A - Imidazomethylene dyes - Google Patents
Imidazomethylene dyes Download PDFInfo
- Publication number
- US4472581A US4472581A US06/407,892 US40789282A US4472581A US 4472581 A US4472581 A US 4472581A US 40789282 A US40789282 A US 40789282A US 4472581 A US4472581 A US 4472581A
- Authority
- US
- United States
- Prior art keywords
- dye
- alkyl
- dyes
- phenyl
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000975 dye Substances 0.000 title claims abstract description 61
- 150000003254 radicals Chemical class 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 239000001018 xanthene dye Substances 0.000 claims abstract description 8
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 5
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- -1 2-ethyl Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- KXKVVKMADLTVSK-UHFFFAOYSA-N (5-methylidene-2-phenylimidazol-4-yl)methanol Chemical group C=C1C(CO)=NC(C=2C=CC=CC=2)=N1 KXKVVKMADLTVSK-UHFFFAOYSA-N 0.000 claims 1
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000004043 dyeing Methods 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 5
- 150000007513 acids Chemical class 0.000 abstract description 4
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000992 solvent dye Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- UQOCEEQQGFOLRM-UHFFFAOYSA-N 2-methylideneimidazole Chemical group C=C1N=CC=N1 UQOCEEQQGFOLRM-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- BJRHJSBSDMOLTA-UHFFFAOYSA-N [3-(hydroxymethyl)-2-phenylimidazol-4-yl]methanol Chemical compound OCN1C(CO)=CN=C1C1=CC=CC=C1 BJRHJSBSDMOLTA-UHFFFAOYSA-N 0.000 description 1
- CIZIDJCTTRZYBO-UHFFFAOYSA-N [4-(hydroxymethyl)-2-methyl-1h-imidazol-5-yl]methanol Chemical compound CC1=NC(CO)=C(CO)N1 CIZIDJCTTRZYBO-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- JMCKWTQLJNQCTD-UHFFFAOYSA-N spirit blue Chemical compound Cl.C=1C=C(C(=C2C=CC(C=C2)=NC=2C=CC=CC=2)C=2C=CC(NC=3C=CC=CC=3)=CC=2)C=CC=1NC1=CC=CC=C1 JMCKWTQLJNQCTD-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B25/00—Quinophthalones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
Definitions
- the present invention relates to cationic dyes which contain bismethyleneimidazole groups, and to their use.
- Cationic dyes which contain methyleneimidazole groups have been proposed (U.S. patent application Ser. No. 233,479), the dyes being obtained by reacting a neutral dye with an imidazole and formaldehyde. These dyes, when they are used for wet-end dyeing of paper, give bleeding-fast dyeings coupled with low contamination of the effluent.
- a and A' may be identical or different and are each a monovalent radical of a dye from the series comprising the azo or quinophthalone dyes, or A and A' independently of one another are each one of the radicals of the formulae ##STR4##
- R is C 1 -C 6 -alkyl, benzyl or aryl
- R 1 is hydrogen
- D' and D" are respectively a monovalent and a divalent radical of a dye from the series comprising the triphenylmethane or xanthene dyes
- n is an integer ⁇ 1
- m is an integer ⁇ 1, the sum (n+m) being ⁇ 10 on average.
- the substituents D'--CH 2 --, --D"--CH 2 -- and R-- are bonded to carbon atoms of the imidazole ring, and, furthermore, the --CH 2 groups of D'--CH 2 -- and --CH 2 --D"-- are bonded to carbon atoms of the aromatic rings of D"-- and --D"-- respectively.
- Preferred dyes I are those in which A and A' are each a quinophthalone radical or D' and D" are each the radical of a triphenylmethane or xanthene dye, the sum (m+n) being ⁇ 10 on average, preferably ⁇ 8.
- the dyes I when they are used for wet-end dyeing of paper, give bleeding-fast dyeings and a colorless effluent. They are from slightly to readily soluble in dilute acids, eg. 5-30% strength by weight acetic acid, propionic acid, methoxyacetic acid or methanesulfonic acid.
- the dyes I are obtained by condensing an appropriate dye D'H ( ⁇ D"H 2 ) (IV) with a bifunctional imidazole, preferably a bishydroxymethylimidazole V, in the presence of an acidic agent; ##STR5##
- R 1 is hydrogen, C 1 -C 4 -alkyl or aryl
- 2 of the radicals R are --CH 2 --OH and the remaining radical R is C 1 -C 6 -alkyl, aryl, eg. phenyl, or benzyl.
- Preferred imidazoles V are those derived from 2-C 1 -C 6 -alkylimidazoles, eg. 2-methylimidazole or 2-ethylimidazole, and from 2-arylimidazoles, eg. 2-phenylimidazole.
- the molar ratio of IV to V is as a rule from 1:0.8 to 1:2.0, preferably from 1:1 to 1:1.2.
- the reaction is carried out in general at from 0 to 50, preferably from 5 to 20, °C.
- the reaction time is as a rule from 2 to 20 hours, and is chosen so that the resulting dye I is still readily soluble in dilute acids.
- the reaction time depends in particular on dye IV.
- a readily soluble dye is obtained if C.I. Solvent Dye, C.I. No. 45,195, is stirred with the imidazole V in 96% strength by weight sulfuric acid for 6 hours at from 20° to 25° C.
- a dye which contains more than one radical (ring) capable of reacting with the hydroxymethyl groups in V is used as IV, eg. the xanthene dye C.I. No. 45,195
- reaction with the bifunctional imidazole V gives a product I which contains more than 2 dye radicals, ie. n and/or m>1.
- the products are polymeric dyes which are only slightly soluble, if at all, in dilute acid.
- dyes where (n+m) ⁇ 10, in particular ⁇ 8 are still readily soluble, and those where (m+n) ⁇ 6 are particularly readily soluble.
- suitable terminal groups for the polymeric dyes of the formula I are --OH and --D'.
- Acidic agents which are suitable for the process and which may simultaneously serve as the reaction medium are, for example, 80-100% strength by weight sulfuric acid or phosphoric acid, with or without agents which split off water, eg. sulfur trioxide (oleum), phosphorus pentoxide, metaphosphoric acid, polyphosphoric acid, acetic anhydride, benzenesulfonic acid or toluenesulfonic acid.
- a preferred acidic medium which may simultaneously serve as the reaction medium is 96-100% strength by weight sulfuric acid, not more than 12% strength by weight oleum or a mixture of 85% strength phosphoric acid and phosphorus pentoxide.
- the reaction mixture is discharged onto water or ice/water, and the dye is precipitated as the free base by adding a basic agent, eg. sodium hydroxide solution, potassium hydroxide solution or ammonia, and is separated off by filtration and dried, or processed further in the form of the water-moist press cake.
- a basic agent eg. sodium hydroxide solution, potassium hydroxide solution or ammonia
- Particularly preferred dyes are those of the formulae ##STR6## where R' and R" are each C 1 -C 3 -alkyl, p is from 3 to 6 on average, E' is --OH and E is --H or 2-phenyl-4-hydroxymethyl-4-methyleneimidazole.
- the molar ratio of dye to imidazole is 5:6.
- the dye is insoluble in organic solvents, such as methanol, ethanol of chlorobenzene, but readily soluble in dilute acids, such as acetic acid, propionic acid, methoxyacetic acid or methanesulfonic acid.
- organic solvents such as methanol, ethanol of chlorobenzene
- dilute acids such as acetic acid, propionic acid, methoxyacetic acid or methanesulfonic acid.
- Example 1 The procedure described in Example 1 is followed, except that the dye of the formula ##STR8## is used instead of C.I. Solvent Dye No. 45,195.
- the molar ratio of starting dye to imidazole is 5:5.
- ⁇ max 524 nm (in 10% strength acetic acid).
- the molar ratio of starting dye to imidazole is 3:4.
- Example 1 The procedure described in Example 1 is followed, except that 9 parts of 2-methyl-4,5-dihydroxymethylimidazole are used instead of 2-phenyl-4,5-dihydroxymethylimidazole.
- the molar ratio of starting dye to imidazole is 5:6.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Coloring (AREA)
- Luminescent Compositions (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3133391 | 1981-08-24 | ||
| DE19813133391 DE3133391A1 (de) | 1981-08-24 | 1981-08-24 | Kationische farbstoffe |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4472581A true US4472581A (en) | 1984-09-18 |
Family
ID=6139973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/407,892 Expired - Lifetime US4472581A (en) | 1981-08-24 | 1982-08-13 | Imidazomethylene dyes |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4472581A (enExample) |
| EP (1) | EP0073008B1 (enExample) |
| JP (1) | JPS5838763A (enExample) |
| DE (2) | DE3133391A1 (enExample) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212312A (en) * | 1980-12-23 | 1993-05-18 | Ciba-Geigy Ag | Vattable and non-vattable quinoid dyes |
| US20070169294A1 (en) * | 2006-01-23 | 2007-07-26 | Cieri Christopher W | Golf club cleaning device |
| US20080209653A1 (en) * | 2006-01-23 | 2008-09-04 | Cieri Christopher W | Golf club cleaning device |
| US20080210590A1 (en) * | 2006-01-23 | 2008-09-04 | Cieri Christopher W | Golf club cleaning device and associated storage device |
| US20080237087A1 (en) * | 2006-01-23 | 2008-10-02 | Cieri Christopher W | Golf club cleaning device and associated storage device |
| US20110083293A1 (en) * | 2008-05-13 | 2011-04-14 | Cieri Christopher W | Golf club cleaning device |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3810958A1 (de) * | 1988-03-31 | 1989-10-12 | Basf Ag | Tinten fuer ink-jet-aufzeichnungsverfahren |
| JP6255482B2 (ja) * | 2014-03-27 | 2017-12-27 | 富士フイルム株式会社 | 化合物、着色組成物、インクジェット記録用インク、インクジェット記録方法、インクジェットプリンタカートリッジ、インクジェット記録物、カラーフィルタ、カラートナー、及び転写用インク |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3592806A (en) * | 1966-12-19 | 1971-07-13 | Hodogaya Chemical Co Ltd | Basic azo dyestuffs containing a quaternized n-alkyl-n - beta-(imidazolyl) lower alkylarylamine group |
| GB1404595A (en) * | 1972-04-13 | 1975-09-03 | Ici Ltd | Water-sobuble quinophthalone dyes |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1266898B (de) * | 1961-04-15 | 1968-04-25 | Basf Ag | Verfahren zur Herstellung von Farbstoffen der Azo-, Anthrachinon- und Phthalocyaninreihe |
| DE2046785A1 (en) * | 1970-09-23 | 1972-03-30 | Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen | Basic mono-azo dyes - for synthetic fibres, cotton silk, leather, paper and paints |
| DE3006013A1 (de) * | 1980-02-18 | 1981-08-20 | Basf Ag, 6700 Ludwigshafen | Imidazolylemethylengruppen enthaltende farbstoffe und deren verwendung |
-
1981
- 1981-08-24 DE DE19813133391 patent/DE3133391A1/de not_active Withdrawn
-
1982
- 1982-08-13 US US06/407,892 patent/US4472581A/en not_active Expired - Lifetime
- 1982-08-17 JP JP57141778A patent/JPS5838763A/ja active Granted
- 1982-08-18 DE DE8282107503T patent/DE3261203D1/de not_active Expired
- 1982-08-18 EP EP82107503A patent/EP0073008B1/de not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3592806A (en) * | 1966-12-19 | 1971-07-13 | Hodogaya Chemical Co Ltd | Basic azo dyestuffs containing a quaternized n-alkyl-n - beta-(imidazolyl) lower alkylarylamine group |
| GB1404595A (en) * | 1972-04-13 | 1975-09-03 | Ici Ltd | Water-sobuble quinophthalone dyes |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212312A (en) * | 1980-12-23 | 1993-05-18 | Ciba-Geigy Ag | Vattable and non-vattable quinoid dyes |
| US20070169294A1 (en) * | 2006-01-23 | 2007-07-26 | Cieri Christopher W | Golf club cleaning device |
| US20080209653A1 (en) * | 2006-01-23 | 2008-09-04 | Cieri Christopher W | Golf club cleaning device |
| US20080210590A1 (en) * | 2006-01-23 | 2008-09-04 | Cieri Christopher W | Golf club cleaning device and associated storage device |
| US20080237087A1 (en) * | 2006-01-23 | 2008-10-02 | Cieri Christopher W | Golf club cleaning device and associated storage device |
| US7841037B2 (en) | 2006-01-23 | 2010-11-30 | Exsite Golf, Inc. | Golf club cleaning device |
| US7904986B2 (en) | 2006-01-23 | 2011-03-15 | Exsite Golf, Inc. | Golf club cleaning device |
| US20110083293A1 (en) * | 2008-05-13 | 2011-04-14 | Cieri Christopher W | Golf club cleaning device |
| US8393041B2 (en) | 2008-05-13 | 2013-03-12 | Exsite Golf, Inc. | Golf club cleaning device |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0073008A3 (en) | 1983-05-25 |
| DE3133391A1 (de) | 1983-03-10 |
| EP0073008A2 (de) | 1983-03-02 |
| DE3261203D1 (en) | 1984-12-13 |
| JPH044345B2 (enExample) | 1992-01-28 |
| JPS5838763A (ja) | 1983-03-07 |
| EP0073008B1 (de) | 1984-11-07 |
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Legal Events
| Date | Code | Title | Description |
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